External Electric Field Will Control the Selectivity of Enzymatic-Like Bond Activations

Shaik, Sason; Visser, Sam P. de; Kumar, Devesh

doi:10.1021/ja047432k

Cited by 280 publications

(316 citation statements)

References 31 publications

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“…[1,2] We think this general feature can be stated as a selection rule: external electric fields oriented along the "reaction axis", the axis along which the bonding changes occur, cause acceleration/retardation of the reaction rate by preferential lowering/raising the transition state, depending on the relative direction of the field to the electronic flow.…”

Section: A Valence Bond Model For the Eef Effect On Rate And Mechanismentioning

confidence: 99%

“…We have started this study as part of an exploratory program of the potential of controlling reactivity patterns by oriented EEFs, [1,2] and chose to focus here on the DA reaction as a candidate for EEF catalysis, because of its immense importance in chemistry [3] and its impact on mechanistic thinking ever since its discovery in the 1920s. [4][5][6] Indeed, the DA reaction has become a chemical icon, because of its unrivaled applicability and deep conceptual implications.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, the Jerusalem group showed [1] that oriented EEFs can control the regioselectivity of propene oxidation by a model active species of cytochrome P450. Simply reversing the EEF direction along the Fe = O bond of the active species leads either to selective CÀH activation or to C=C activation.…”

Section: Introductionmentioning

confidence: 99%

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Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the endo/exo Selectivity

et al. 2010

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Herein we demonstrate that an external electric field (EEF) acts as an accessory catalyst/inhibitor for Diels-Alder (DA) reactions. When the EEF is oriented along the "reaction axis" (the coordinate of approach of the reactants in the reaction path), the barrier of the DA reactions is lowered by a significant amount, equivalent to rate enhancements by 4-6 orders of magnitude. Simply flipping the EEF direction has the opposite effect, and the EEF acts as an inhibitor. Additionally, an EEF oriented perpendicular to the "reaction axis" in the direction of the individual molecule dipoles can change the endo/exo selectivity, favouring one or the other depending on the positive/negative directions of the EEF vis-à-vis the individual molecular dipole. At some critical value of the EEF along the "reaction axis", there is a crossover to a stepwise mechanism that involves a zwitterionic intermediate. The valence bond diagram model is used to comprehend these trends and to derive a selection rule for EEF effects on chemical reactions: an EEF aligned in the direction of the electron flow between the reactants will lower the reaction barrier. It is shown that the exo/endo control by the EEF is not associated with changes in secondary orbital interactions.

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Section: A Valence Bond Model For the Eef Effect On Rate And Mechanismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the endo/exo Selectivity

et al. 2010

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“…If these compounds can reversibly react with the imine by component exchange, the field influences the equilibrium state of constitutional dynamic mixtures of imines. Both amines and aldehydes are exchanged upon formation of a CDL of the corresponding imines, [23] and volatile compounds are more readily expelled from the liquid crystalline film than non-volatiles. Liquid crystalline forming imines are therefore suitable materials to modulate controlled release of volatile organic compounds by application of an electric field and point to the possibility of constructing electric devices that allow fine-tuning of the release rates of individual compounds and compound mixtures as a direct response to an electric signal.…”

Section: Discussionmentioning

confidence: 99%

Electric‐Field Triggered Controlled Release of Bioactive Volatiles from Imine‐Based Liquid Crystalline Phases

Herrmann

Giuseppone

Lehn

2008

Chemistry A European J

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Application of an electric field to liquid crystalline film forming imines with negative dielectric anisotropy, such as N-(4-methoxybenzylidene)-4-butylaniline (MBBA, 1), results in the expulsion of compounds that do not participate in the formation of the liquid crystalline phase. Furthermore, amines and aromatic aldehydes undergo component exchange with the imine by generating constitutional dynamic libraries. The strength of the electric field and the duration of its application to the liquid crystalline film influence the release rate of the expelled compounds and, at the same time, modulate the equilibration of the dynamic libraries. The controlled release of volatile organic molecules with different chemical functionalities from the film was quantified by dynamic headspace analysis. In all cases, higher headspace concentrations were detected in the presence of an electric field. These results point to the possibility of using imine-based liquid crystalline films to build devices for the controlled release of a broad variety of bioactive volatiles as a direct response to an external electric signal.

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“…Finally, it has been hypothesized that biochemical reactions can be controlled by electric fields created in proteins, which can reach up to ±0.01 au. [100][101][102][103][104][105][106] This suggests a possible mechanism of effective biological control of protein CysNO reactivity that takes advantage of the peculiar antagonistic nature of the -SNO group.…”

Section: Antagonistic Nature Of Ch 3 Snomentioning

confidence: 99%

Toward reliable modeling of S-nitrosothiol chemistry: Structure and properties of methyl thionitrite (CH3SNO), an S-nitrosocysteine model

Khomyakov

Timerghazin

2017

The Journal of Chemical Physics

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Methyl thionitrite CH 3 SNO is an important model of S-nitrosated cysteine aminoacid residue (CysNO), a ubiquitous biological S-nitrosothiol (RSNO) involved in numerous physiological processes. As such, CH 3 SNO can provide insights into the intrinsic properties of the -SNO group in CysNO, in particular, its weak and labile S-N bond. Here, we report an ab initio computational investigation of the structure and properties of CH 3 SNO using a composite Feller-Peterson-Dixon (FPD) scheme based on the explicitly-correlated coupled cluster with single, double, and perturbative excitations calculations extrapolated to the complete basis set limit, CCSD(T)-F12/CBS, with a number of additive corrections for the effects of quadruple excitations, core-valence correlation, scalar-relativistic and spin-orbit effects, as well as harmonic zero-point vibrational energy (ZPE) with an anharmonicity correction. These calculations suggest that the S-N bond in CH 3 SNO is significantly elongated (1.814 Å), has low stretching frequency and dissociation energy values,

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External Electric Field Will Control the Selectivity of Enzymatic-Like Bond Activations

Cited by 280 publications

References 31 publications

Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the endo/exo Selectivity

Oriented Electric Fields Accelerate Diels–Alder Reactions and Control the endo/exo Selectivity

Electric‐Field Triggered Controlled Release of Bioactive Volatiles from Imine‐Based Liquid Crystalline Phases

Toward reliable modeling of S-nitrosothiol chemistry: Structure and properties of methyl thionitrite (CH3SNO), an S-nitrosocysteine model

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